Paul Jehn

The Ground Water Protection Council

www.gwpc.org
In 2010, U.S. shale gas production reached 4.87 Tcf (23 

percent of total U.S. natural gas production), compared with 

0.39 Tcf in 2000. This shows both the rapid growth and 

absolute importance of the shale gas resource to the United 

States. Rising production from shale gas resources has been 

credited with both lower natural gas prices and declining 

dependence on imported natural gas. As is often the case with 

resource development, shale gas production also has raised 

local environmental concerns, largely centering on the amount 

of water used in the fracturing process and the need to 

handle, recycle, and treat fracturing fluids in a manner that 

addresses the risk of spills that can potentially affect water 

quality. EIA's Annual Energy Outlook 2011 Reference case also 

reflects the growing importance of U.S. shale gas. It projects 

that shale gas will account for about 46 percent of U.S. natural 

gas production in 2035.

http://www.eia.doe.gov/todayinenergy/detail.cfm?id=811

 All land use activities have the potential to 

impact groundwater

 Many land use activities use similar chemicals 

and compounds

 Some of these chemicals and compounds can 

occur naturally
 Chemicals used in HydroFrac operations

 Geochemistry of the formation to be HF

 Geochemistry of the USDW

 Chemicals used in homes and nearby industry

 Chemicals and compounds common to all of 

the above 

 Baseline and trend monitoring

 Indicator chemicals


Compound Percent PPM

Surfactant 0.0850 850

KCl 0.0600 600

Gelling Agent 0.0560 560

Scale Inhibitor 0.0430 430

pH Adjusting Agent 0.0110 110

Breaker 0.0100 100

Crosslinker 0.0070 70

Iron Control 0.0040 40

Corrosion Inhibitor 0.0020 20

Biocide 0.0010 10

Acid 0.1230 1230

Friction Reducer 0.0880 880
 Surfactant: Glycol Ether

 Gelling Agents: Benzene, Ethyl Benzene, 

Xlyenes, Toluene, Methyl Tert-Butyl Ether

 Biocides: Polynuclear Aromatics and Polycyclic 

Organics

 Clay Stabilizers: Methanol

 Crosslinkers: Formic Acid, Ammonium 

Chloride

 Zirconium Nitrate and Sulfate

 Buffers: Acetic Acid

 Acidizing Treatment: Methanol
 Acid

 Iron Control Agent

 Corrosion Inhibitor

 Bactericide

 Scale Inhibitor

 Friction Reducer

See PDF file for more detail

 Uranium (10- 100ppm, U4+, U6+), Zinc, Iron, Sr, 

Cl, Na, Ca, Ba, As, Co, Pb, Cr, V

 High TDS , Specific Conductance

 For more information on the geochemistry of the 

Marcellus Shale see: 

http://connect.sierraclub.org/app/render/go.asp

x?g=9664c52f-f718-4790-810a- 667acb1aaf42&xsl=tp_SocialObjects_ObjectType

_SIERRA_CLUB_ONLINE_COMMUNITIES_RESOURCE

S_PUBLIC.xslt&id=9664C52F-F718-4790-810A- 667ACB1AAF42&cons_id=&ts=1303506080&sig

nature=d8b40fb3068d36e7062d5d1d5815ca86

 NORM
 NORM occurs naturally throughout our 

environment from the sun and deep space, in 

our bodies, the food we eat, the places we 

live and work, and the ground we live on. 

Certain industrial processes, however, can 

cause NORM to accumulate at concentrations 

greater than natural background levels. The 

petroleum industry is one of several 

industries that generate large volumes of 

NORM-bearing wastes. 
 The petroleum industry, is one of several industries 

that generate large volumes of NORM-bearing 

wastes. The sources of most of the radioactivity in 

petroleum industry wastes are the isotopes formed 

from the radioactive decay of uranium-238 (U-238) 

and thorium-232 (Th-232), which are naturally 

present in the subsurface formations from which oil 

and gas are extracted. The primary radionuclide of 

concern in NORM wastes is radium-226 of the U-238 

decay series. Radium-228 of the Th-232 decay 

series also occurs in NORM waste, but usually at 

lower concentrations. Other radionuclides of concern 

include those that form from the decay of Ra-226 

and Ra-228.

• Units

– μRoentgen/hr (radiation exposure)

– μRem/hr (also units of Sv or sieverts) 

(human dosage)

– pCi/g (concentration per mass)

– pCi/m

– Rads (also units of grays) 

– μ = micro = millionth

– p = pico = billionth
Radium is concentrated in scale and 

sludge when precipated with 

Ba-, Sr-, or Ca-SO4

http://www.rrc.state.tx.us/environmen

tal/publications/norm/NORMRRCsemin

ar04.pdf
Radium radionuclides emit alpha and beta particles as well as gamma rays. The 

radiation emitted from a Radium 226 atom is 96% alpha particles and 4% gamma 

rays. The alpha particle is the most dangerous particle associated with NORM. 

Alpha particles are helium nuclei. Alpha particles travel short distances in air, of only 

2-3 centimeters and cannot penetrate through a dead layer of skin on the human 

body. However, alpha particles are "bone seekers" due to Radium possessing a 

high affinity for Chloride ions. In the case that Radium atoms are not expelled from 

the body, they concentrate in areas where Chloride ions are prevalent, such as 

bone tissue. The half-life for Radium 226 is approximately 1620 years, and will 

remain in the body for the lifetime of the human; a significant length of time to cause 

damage.

Beta particles are high energy electrons or positrons. They are in the middle of the 

scale in terms of ionizing potential and penetrating power, being stopped by a few 

millimeters of aluminum foil. This radiation is a small portion of the total emitted 

during Radium 266 decay. Radium 228 emits 100% beta particles, which are also a 

concern for human health through inhalation and ingestion. Beta particles are 

electrons or positrons and can travel farther than alpha particles in air.

The gamma rays emitted from Radium 226, accounting for 4% of the radiation are 

harmful to humans with sufficient exposure. Gamma rays are highly penetrating and 

some can pass through metals, so Geiger counters with a scintillation probe are 

used to measure gamma ray exposures when monitoring for NORM.
 The petroleum industry waste streams most 

likely to contain elevated radium concentrations 

include produced water, scale, and sludge. 

Radium, which is slightly soluble, can be 

mobilized in the liquid phases of a subsurface 

formation and transported to the surface in the 

produced water stream. As the produced water is 

brought to the surface, some of the dissolved 

radium precipitates out in solid form. Most 

commonly, the radium coprecipitates with 

barium sulfate, a hard and relatively insoluble 

scale deposit; however, it also can coprecipitate to form other complex sulfates and carbonates.
Measurement of total radioactivity with a hand-held 

radiation detection instrument permits rapid assessment of a site for NORM contamination, but 

site cleanup criteria and waste disposal options are 

based on actual concentrations of radium isotopes. 

Some specialized field instruments permit rapid estimates of the concentration of radium isotopes, but such estimates require confirmation by careful laboratory analysis of selected subsets of samples. 

Radium concentrations are generally reported as 

picocuries/gram (pCi/g) of solid material or picocuries/liter (pCi/L) of water or air. A picocurie equals 2.22 disintegrations-per-minute (dpm). 
 Geothermal Energy Production Wastes

 Oil and Gas Production Wastes

 Coal Ash

 Mining Wastes: uranium, fertilizer, aluminum

◦ http://www.epa.gov/radiation/tenorm/sources.htm

l#summary-table
http://www.epa.gov/radiation/tenor

m/sources.html#summary-table
 http://norm.iogcc.state.ok.us/
 U.S. Department of 

Energy, Office of Fossil 

Energy http://www.fe.doe.gov/

 American Petroleum

Institute http://api-ec.api.org/

 Nuclear Regulatory 

Commission http://www.nrc.gov/

 U.S. Environmental 

Protection Agency 

http://www.epa.gov/radiation/tenorm/

 Interagency Steering 

Committee on 

Radiation Standards

http://www.iscors.org/

 International 

Commission on 

Radiological Protection

http://www.icrp.org/

 U.S. Geological 

Survey -- NORM Fact 

Sheet

http://pubs.usgs.gov/fs/fs-0142-99/fs-0142-

99.pdf
Can methane be use as an indicator for 

impacts to groundwater from HF operations?
 CH4

 Colorless, odorless gas

 Principal component of natural gas

 The firedamp of coal mines is chiefly methane

 Anaerobic bacterial decomposition of plant 

and animal matter, such as occurs under 

water, produces marsh gas, which is also 

methane.

 Ref: http://scifun.chem.wisc.edu/chemweek/methane/methane.html
Methane gas occurs naturally in groundwater aquifers in 

most geological sedimentary basins worldwide, including 

here in Alberta. Methane gas exists in a dissolved state in 

groundwater underground and will “bubble out” when 

pumped to the surface. For those on private water well 

supplies, spurting taps is a common result of this 

phenomenon.

Alberta Environment oversees a network of over 250 

groundwater monitoring wells spread across the province. A 

monitoring program was initiated in 2006 to better 

understand the quality of groundwater in Alberta. The 

monitoring wells are tested for a variety of water quality 

parameters, including methane gas. A total of 126 wells 

have been accessed for gas sampling to date. Wells will be 

sampled every few years to monitor long-term trends.

http://environment.alberta.ca/02883.html
 Out of the 126 wells visited, 38 wells 

contained appreciable concentrations of 

methane gas (>3000 ppmv), 32 wells 

contained minor concentrations (<3000 

ppmv) and 56 wells contained no measurable 

amounts of gas. Many wells with methane 

gas lie outside the coalbed methane 

development areas in Alberta and many wells 

with no gas lie within coalbed methane 

development areas.

http://environment.alberta.ca/02883.html
In many places, groundwater naturally contains 

significant concentrations of methane. High 

concentrations of methane, sometimes at 

explosive levels, are known to occur in both NY 

and PA, and elsewhere (Osborn 2010; WV USGS 

2006). 

This makes the mere detection of methane in 

private water wells an inadequate test for 

determining whether gas drilling has caused 

water contamination.
Typical Composition of Natural Gas

 MethaneCH4 70-90%

 Ethane C2H6 0-20%

 Propane C3H8

 Butane C4H10

 Carbon Dioxide CO2 0-8%

 Oxygen O2 0-0.2%

 NitrogenN2 0-5%

 Hydrogen sulphide H2S 0-5%

 Rare gases A, He, Ne, Xe trace
 Methane gas can 

be biogenic or thermogenic depending on its 

origin.

 Biogenic methane is produced by subsurface 

bacteria and is a common natural source of 

methane gas in groundwater aquifers used for 

water well supplies;

 Thermogenic methane gas is produced at greater depths through high pressure and temperature 

processes and is characteristic of deep oil & gas 

reservoirs that conventional energy wells tap 

into; and

 CBM gas tends to fall somewhere between these 

two components.
 Biogenic

 Thermogenic

Two distinct processes produce hydrocarbon gas: biogenic and 

thermogenic degradation of organic matter. Biogenic gas is formed at shallow depths and low temperatures by anaerobic bacterial 

decomposition of sedimentary organic matter. In contrast, 

thermogenic gas is formed at deeper depths by:

 (1) thermal cracking of sedimentary organic matter into 

hydrocarbon liquids and gas (this gas is co-genetic with oil, and is called "primary" thermogenic gas ), and

 (2) thermal cracking of oil at high temperatures into gas 

("secondary" thermogenic gas) and pyrobitumen.

 Biogenic gas is very dry (i.e., it consists almost entirely of 

methane). In contrast, thermogenic gas can be dry, or can contain significant concentrations of "wet gas" components 

(ethane, propane, butanes) and condensate (C5+hydrocarbons).
Various data analyses can be used in conjunction to help 

determine whether gas in a monitoring well is of biogenic or 

thermogenic origin, or a mixture of the two.

Methane gas typically contains a small amount of ethane. 

The proportion of methane to ethane in a gas can help 

determine its origin. Biogenic gas typically contains above 

1000 times more methane than ethane. In addition, isotope 

data can also be used to help determine whether a gas is 

biogenic or thermogenic. Carbon isotope ratios have been reported for monitoring wells containing concentrations of 

methane gas above 3000 ppmv. Isotope values tend not to be reliable below this concentration.

 http://environment.alberta.ca/02883.html
http://environment.alberta.ca/02883.h

tml
Thermogenic gas components (methane, 

ethane, propane) generated at a given thermal 

maturity contain, on average, isotopically

heavier carbon than do the corresponding gas 

components generated at a lower thermal 

maturity. Relationships between gas isotopic 

compositions and source maturity have been 

calibrated, allowing the vitrinite reflectance 

equivalent (VRe) of the gas source to be 

estimated from the gas geochemistry (Faber, 

1987; Berner and Faber, 1988; Berner, 1989).
 Biogenic methane, on average, contains isotopically lighter 

carbon (i.e., is more depleted in 13C) than thermogenic

methane. Biogenic gas is also drier than many thermogenic

gases. Ranges of gas composition corresponding to (i) 

bacterial gas, (ii) thermogenic, oil-associated gas, (iii) dry, 

post-mature thermogenic gas, and (iv) gas of mixed 

biogenic/thermogenic origin have been defined, facilitating 

the interpretation of gas compositional data (e.g., Schoell, 

1983, 1988; Faber et al., 1992; Whiticar, 1994). In cases 

where gas seeps may be derived from biogenic 

decomposition of anthropogenic wastes ("landfill" gases), 

other tracers, such as 14C and tritium can be used to 

distinguish landfill gases from older biogenic gases 

unassociated with anthropogenic waste (Coleman, 1995).
These techniques involve measurement of stable 

isotopes of carbon (C) and hydrogen (H) within 

methane (CH4) and related compounds, such as 

carbon dioxide (CO2), water (H2O), ethane (C2H6) 

and other hydrocarbons. The goal of this type of 

monitoring is to aid water well owners who wish to 

distinguish methane contamination that arises 

naturally from contamination resulting from 

nearby drilling activities

http://wri.eas.cornell.edu/index_18_2774977203.

pdf
 While stable isotope monitoring can provide 

valuable information in the event of water 

contamination, it also has significant limitations. 

Conclusive results generally require extensive 

and coordinated sampling, incorporation of 

additional data related to geology, hydrology, 

and chemistry, and expertise in data 

interpretation.

For more information on Isotopes see 

http://wri.eas.cornell.edu/index_18_2774977203.

pdf
“Diagnosing methane contamination in 

groundwater and private drinking water wells is 

possible with the help of isotopic analyses. 

However, it is not necessarily an easy task, 

and can be limited by significant uncertainty.”

http://wri.eas.cornell.edu/index_18_27749772

03.pdf
Trend Monitoring, Pre-Frac Baseline, Post 

Frac Analysis and Indicator Chemicals
 Major cations and anions

 pH

 Specific Conductance

 Total Dissolved Solids

 Nitrates

 Dissolved methane

 Benzene, Toluene, Ethyl benzene, Xylene (BTEX)/ Diesel Range Organics (DRO)/ Gasoline Range Organics (GRO)

 VOC’s and Semi-VOC ‘s

 Total Petroleum Hydrocarbons or Oil & Grease (HEM)

 Arsenic

 Barium

 Calcium

 Chromium

 Iron

 Magnesium
 Selenium

 Boron

 Sodium

 Chloride

 Potassium

 Bicarbonate

 Dissolved Methane

 NORM
 If free gas or a dissolved methane 

concentration level greater than two (2) 

milligrams per liter (mg/l) is detected in a 

water well, gas compositional analysis and 

stable isotope analysis of the methane 

(carbon and deuterium) should be performed 

to determine gas type. 
 If the test results indicate biogenic gas, no 

further isotopic testing is necessary.

 If the test results indicate thermogenic or a 

mixture of thermogenic and biogenic gas 

additional isotopic analysis should be 

performed to determine the source of the 

gas.
 State Public Water Supply Records

 State Monitoring Networks

 State Permit Compliance Data

 State Oil and Gas Agencies

 US EPA: STORET 

http://www.epa.gov/STORET/

 USGS: http://water.usgs.gov/owq/
 Baseline monitoring is necessary 

◦ Is there data to show trends in data before the HF 

operation?

 Post HF monitoring

◦ First level 

 Methane

 NORM
 RBDMS Water
 http://www.gaschem.com/determ.html

 Berner, U., and E. Faber, 1988, Maturity related mixing model for methane, ethane and propane, based on carbon isotopes: Org. Geochem., v. 13, p. 67-72.

 Coleman, D. D., C.-L. Liu, K. C. Hackley, and S. R. Pelphrey, 1995, Isotopic Identification of Landfill Methane: Environmental Geosciences, v. 2, p. 95-103.

 Faber, E., W. J. Stahl, and M. J. Whiticar, 1992, Distinction of bacterial and 

thermogenic hydrocarbon gases, in R. Vially, ed., Bacterial Gas, Paris, Editions 

Technip, p. 63-74.

 Rice, D. D., 1993, Biogenic gas: controls, habitats, and resource potential, in D. G. 

Howell, ed., The Future of Energy Gases - U.S. Geological Survey Professional Paper 1570, Washington, United States Government Printing Office, p. 583-606.

 Schoell, M., 1983, Genetic characterization of natural gases: AAPG Bulletin, v. 67, 

p. 2225-2238.

 Schoell, M., 1988, Multiple origins of methane in the earth: Chemical Geology, v. 

71, p. 1-10.

 Whiticar, M. J., 1994, Correlation of natural gases with their sources, in L. B. 

Magoon, and W. G. Dow, eds., The Petroleum System, From Source to Trap, AAPG, 

p. 261-283.

 http://wri.eas.cornell.edu/index_18_2774977203.pdf The Role of Isotopes in Monitoring Water Quality Impacts Associated with Shale Gas Drilling